Process for the constructive conversion of hydrocarbons



H. R. BERRY. PROCESS FOR THE CONSTRUCTIVE CONVERSION OIF HYDROCARBONS.

APPLICATlON FILED AUG. 10. i922.

PatentedSept. 19, 1922 2 SHEETS-SHEET lK ANN@ Jam

IN VEN TUR BY AZTORNEYS H. R. BERRY.

PROCESS FOR THE CONSTRUOTIVE CONVERSION OF HYDROOARBONS.

APPLICATION FILED AUG. l0. i922.

Patentedept. 19, 1922..

2 sHEETsHET 2.

lAQlG.

MUTE@ .WW kum.

NVENTR BY TTRNE'YJ UWM ons( dugg( Patented Sept.. i9, liZ., v

sra 'ar HAROLD R'. BERRY, l0F BROOKLYN', NEW YORK.

rnoonss non THE oonsrnuo'rivn CONVERSION or irrnaocannon's.

Application ined. August 1o, v1922,. serial No. 550,958.

To all 'whom't may concern: ing of various substantially different hydro- Be it known that-l, HARoLn R. BERRY, citicarbon compounds in heterogeneous relazen ot the llnited States, residing at Brooktionship and their readjustment into a pre- 50 lyn, in the county of Kings and State ot' determined and selected hydrocarbon prod- 5 New York, have invented certain new and uct. which for all commercial purposes is useful Improvements in Processes :tor the substantially uniform or commercially ho- Constructive Conversion of Hydrocarbons, mogenous. ot' ivhich the following is a speciication. The preferred method tor accomplishing 55 This invention pertains toa process for these results includes any kind oi' means 'l0 the constructive conversion ot hydrocarbons. for causing the various' hydrocarbon com- The purpose is the conversion ot' the oil and pounds to be hydrogenized at or above their othei` materials treated into a hydrocarbon points of molecular instability, and for Withproduct of the type and gravity selected and drawingsuch part of the treated mass as 50 predetermined, has attained desired hydrogenization. The

l5 Essential diiierentiation is claimed trom process vcontinues treatment ot the residue fractional distillation, and the practiced until total desired hydrogenization or the methods of oil cracking'. entire mass is etl'ected. N

The materials used are crude petroleum `v`It is preferred to accomplish this result 65 or its heavy-gravity fractions, in conjunc' byutilirirng` a pressure, temperature and tion With natural gas, overly rareied resultgravityl Zonek of such character that it Will ants of fractional distillation, artificial not receive and pass hydrocarbon products grasos, preferably water gas or hydrogen, until they have been reconstituted Ainto a derived as a product from super-heated steam `state which'is commercially uniform or sub- 70 in contact with suitable metallic oxidizing" stantiallyhomogeneous; p j y y reagents, or otherwise. Anyot' these maybe y The process contemplates thel vaporizaused in combination. and with or without tion of each'differentiated compound of the the addition ot' Water or steam. 4 oil mass, as its respective boiling-pointrtem- The process contemplates operation with perature is attained,"the amount ot pressure .75 or Without pressure, but a method is subutilized being suliicient'to raise thewboiling' mitted Jfor determining the proper' coetlipointfto' equal orexceed the temperature.otr cients 'of pressure and temperaturerequiremolecular instability", whereby'liydrogrenizaF` ments, dependent upon analysis ot the oil tionV- and molecular readjustm'ent occur` Y y to be treated` 1 Y 1 As each succeeding' Icompound attainsva- 80 The required heat for the operation .isky porizati'on, it ceases to' tollmvthe directionl supplied preferably by superhcating the.,v of the yoi l,f'but countertloxvs, as vapor,

gaseous'material employed. the' liydrogenous,:gaseous material'used in ln carrying' out the invention, the liquid the operation. vraud encounters constantly and gaseous `materials are preferably cooler temperature zones` v counterloived against each other in any suit- The ultimate and coolest te'mperature is 4o able apparatus, in such manner that the oil regulated and yfmaintained at' the boiling: introduced tor treatment issubjected Vto point ot the selected and vpredeterminedlA ever-increasing` temperature, and the gaseous product.` Such compounds ot the oil m'ass material is subjected to ever-decreasing` temas are not sufficiently hydrogenizedf during W peresture` as heat is gradually, though con-l vapori'zation, liqueicyvand iiovv with the oil 35 stantly, transferred to the oil through con mass, and imdergo revai'iorization. A The tact. process 'continues until attainment' of exitV The process contemplates 'tre mistabilizn conditions is met, when escapement follows.

The operation of the process will be described in connection with the production of a specific product, gasoline, for instance, from heavy petroleum fractions in conjunction with, for instance, natural gas.

The principles and reasons governing the process and its application will be set forth. The apparatus described is` one, among others, capable of being so manipulated as to carry out the process and method presented.

The principles underlying this invention are:

l. The specific gravity and the boiling point of the hydrocarbon found in petroleum, are decreased, by increasing the ratio of the hydrogen content.

The variation of these properties of the hydocarbon compound is illustrated in the following:

H dro- Boiling Specific Compound' geii, point. gravity.

Nonodecane .C1QH40. 14. 93 y 635 F. O. 8122 Octodecane. 14. 96 607 8017 Heptadecane 15.00 578 794 Hexadecane 15. O4 549 .7911

Trideeane. 15. 22 453 775 Undecane. 15. 38 351 7411 Heptane 16. U() 209 7304 As the ratio of hydrogen content in- CIeaSQS, SpeClfiC gl'lVllQS lIlCl bOlllIlg pOlIltS decrease; thus specific gravities and boiling points are raised or lowered inversely with the increase or decrease of the hydrogen content of the molecule.

2. Reason presents but two ways in which this hydrogen ratio can be increased., In an oil composed of so much hydrogen and so much carbon, the ratio of the hydrogen to the mass can be increased either (a) by taking some of the carbon out, in which case the hydrogen sustains an increased ratio to the remaining mass, or (b) by adding hydrogen to the compound (a) is accomplished by so-called cracking; (b) by the methodpresented herein. The product of (a) is largely oleine, smokey and rarely sweet; the product of (b) is sweet, clear, and araine.

3. 'ach hydrocarbon compound occurrentin 'petroleum has distinctive characteristics, distinguishing it from other such co1npounds. The characteristics include, not only diti'erentiations in specific gravities, molecular weights, hydrogen contents, and boiling points, but also characteristic difierences in the tempera-ture required to produce instability of the molecular organization.

In the processes of cracking, by the application of heat and usually, pressure, molecular instability is carried to the point of molecular dismemberment, by which the atomic constituents are thrust asunder.

.bon

There is a correspondent state of interatomic agitation within the molecule for any heat condition established. lVith additional heat, the molecule becomes more and more agita-ted and less stable, resulting, with sufficient heat, in disassociation, but during this period of agitation and non-stability, other elements, properly conditioned, easily enter the oil, with accompanying molecular readjustments. The temperature of instability for each compound, is, then, that temperature, below the cracking point, at which molecular readjustment and incorporation of new elements is most easily effected.

1. The application of pressure, in the heat treatment of a liquid, elevates its boiling point. It is therefore possible to regulate pressure so that the boiling point of a hydrocarbon compound may be elevated to equal or exceed its temperature of molecular instability. In this case, the resultant vapor emanates in a state of instability, and is susceptible of hydrogen assimilation.

5. 'Concerning saturation: it has become quite the practice to use the term saturated compound to indicate a hydrocarbon compound, thoroughly impregnated with the maximum hydrogen coeiicient for the carpresent. In the parafiine series, C-}H2+2, it is found that, given any speciiic carbon content, the hydrogen accompanying the specified carbon quantity is greater in amount in this series than in any Y other.

Paraine-butane. @Hw-17. 2% Hydrogen.

Acetylene-crotonv y 04H5 11. l Aromatics-benzine Parafiine series" is thus customarily used interchangeably with saturated series.

As every constituting member of the oleine series contains 14.28% hydrogen. conversion, throughI hydronization into another olene may nottbe effected,` but the incorporation of hydrogen into its molecule makes it a parafiine.

C4HS+2H=C4HW a para-nine.

Following the sequence of the chief petroleum hydrocarbons in their relationship to the hydrogen molecule H2 we find:

(01031195) +2H= allznn (paraines) In the parafiine compounds the sequence continues,

reaaeio The principle involved is, though the parafine possesses for its carbon content, in comparison with other family groupings, the greatest ratio of hydrogen incorporation; nevertheless, each compound of the parafline series possesses a different and characteristic percentage of hydrogen.

ln the direction of methane the hydrogen content constantly increases and is accompanied by reduced boiling point and specific gravity.

Compound. Hydrogen. B. Pf() sp. gr

Nonodecanc CmHm 14. 93% 330 0. 777 Octodccanc.. a 3u. 14. 95 317 7765 Heptadeeanc. .C11H35. 15. 00 303 776 Hcxadccauc. CIGHM 15. 04 287. 5 7758 Pcntadccanc.. (IHM. 15. 09 270 7756 Tcradccane. 0141150 15. 15 252 775 Tridccanc. ClaHm 15. 22 234 775 Dodccane. CM1-Im 15. 29 214 7745 Undecunc s XHM. 15.38 194 .774

@ne pound or carbon occurrent in tridecane is incorporated with .17% pounds et hydrogen.

Une pound of carbon occurrent incorporated `with .1%3 pounds o Both are para'l'llne.

Both are termed saturated.

v liscussion 'which departs 4rozn customary usagre oi the word, saturation, l find may not ne had this time and under these circumstances, l quote troni: Richter-s @rw garlic Chemist 1y, i922 edition, published by l). Blalristonls 'tion c Qc., vol. l, page 68,

They (carbon compounds) are further classified into saturated and unsaturated compounds. the iirst of these, called also limit compounds or parafhns, the directly united quae .ilent carbon atoms are linked to each other by a single bond, so that 'the number or@ affinities still remaining to ce satislied in chain of n carbon'atorns is 21H-2.- lheir general formula is, therefore, expressed in form ont @n X2-l2, Where X represents the affinities ot' the elements o1' groups directly combined with carbon..97

'ln inorea-sinn the hydrogen content ot the parai'fne and thereby reducing)- its gravity and boiling point, the problem is not that tie carbon content has assimilated all the hydrogen chemically incorporatible with the amount et carbon present. 'li he requirement is to unstabilize the single bond union ot the parailine through inter-atomic activity produced hy the proper coelicient ot heat and pressure. c i

6. rlhe relationship between .hydrogen content, boiling point, andl specific gravity of theparatlines has been noted. The inlinitesirnal increase of'hydrogen content in each succeeding corn ound ot the series, in the direction of met ane, has been shown.

n hexane is hydrogen.

lt may now be stated that any condition or pressure and temperature, maintained in a suitable apparatus, has its coeicient in one 'y together probable that the ascent about by a number oi" reactions. violecular instability, brought about by the heat and pressure conditions, may be followed the occurrence of olene, chain, and other non* parailine structures. Such series, however, being comparatively unstahle at best, ly saturate into the lighter paraines. Llegar/@tion 'of the apparatus its fw/tations.

the accompanying drawings:

igure is a diagrammatic View, inostly in cross-section, of an apparatus operative the process and method presented herein.

igure 2 is a vertical section showing part e generator and iilrnenting; plates. laure 3 a plan view, partly in horisontal section, looking down on the construction shown in Figure 2.

Figure is a section on smaller vscale shoving the manner of assembling the lireclay wall sections.

Figure 5 is view partly in section and partly in elevation, showing the entire ener vtor.

Lilie reference numerals indicate corren spendingn parts in the different ngures the drawing.

From left right in fr the elements of the apparatus are:

generator- B.

rd-a refrigeration systemitha collecting tank-D.

The heater, A, may be o1c any suitable construction. this instance, the walls oir' the heater are constructed oit' {ire-clay and brick within, and steel casing` Wit-hout, and it contains a nest or high-pressure piping, with the heat delivered at the fire box, l, and distributed throughout the interior of the heater. The heater, A, is supplied with any hydrogen-containing gas, for instance natural gas, by means of the certrally located compressor, 2, at desired pressure. The gas is delivered at the top of thc-heater through the pipe, 3. and passes down through the coil system as shown. The small compressor, l, to the left, is utilized for delivering water. at a point adjacent to the delivery point of the gas within the top part of the heater, A., as shown. lf the operation is conducted without the use of steam, the supply is closed in any suitable manner by pet-cock, for instance, as shown. There is generated a temperature, corrected to the pressure used, eX- ceeding the degree of heat required for vaporizing the heavy hydrocarbons contained in the oil to be introduced into the apparatus for treatment. The exit pipe, 5, passes from the bottom most part of the heater, A, and gives exit to the superheated gas under the pressure maintained. The exit pipe, 5, is controlled with a cut-off valve, 6, and ay combined, one-way valve and regulative pressure valve cock, 7, of any suitable character.

There is thus discharged in the bottom of the' second apparatus, B, the heated gas, which ascends through the filmenting construction of the generator. Figs. 2, 3, et, 5 are generator B in greater detail than shown in Fig. 1.

ln Fig. 2 the filmenting member 8 is constructed of any suitably substantial material. Tt may be made of fire-clays, terra cotta, carborundum, metals or other suitable niaterials. It may be of solid or hollow construction. ln the design shown it is hollow and of cast iron construction. lt is equipped with a small hole, 30, centrally located in the dish-shaped side (31) to allow for equalization of pressure conditions.

In this construction the member is cast in two pieces, such as are formed by a plane passing through the circumference and thecenter of both the top and the lower dishshaped side. The two halves after being cast, are welded together at their like edges, constituting thereby the hollow, enclosed, dish-shaped iigure, represented in the drawing by As constituting another part of the unit, there is a circular disk member, (9) constructed of any suitably substantial material. ln the design submitted it is of cast iron.

The disk is equipped with a cent-ral opening of such size as operating conditions require. This circular disk is of larger diameter than that of the dish-shaped or filmenting part, sufficient to allow the circulardisk part to extend over and rest upon the insulating material, 34, within the shell 35.

Circularl disk (9) and the dish-shaped ilmenting member (8) are attached one to the other, having the intervening space (36) of any suitable amount for working condition. The connection is made by any suitable means utilizing any material or materials.

ln the construction illustrated three metal blocks (37) for instance 8 x 2 x are placed on the top of the dish-shaped mein-ber, 8, so that a line bisectingthe length of the blocks will coincide with a radius of the upper or fiat circular side of the dishshaped part, 8, the three blocks being equidistant one from the other. Thus placed, the 'blocks are welded to the top surface of the dish-shaped member, and to the bottom surface of the circular disk, 9.

ln installing'the unit, the insulating wall 34 may be made in a number of pieces. four, for instance, as shown in Figure Lt. When placed in position within the generator, and properly cemented together, the circular disk, 9, may rest upon the top surface so formed. The circular disk does not touch the shell of the generator.

The space (38) between the circumference of disk (9) and the shell provides room for expansion and contraction under the heat conditions maintained; the space thus remaining is filled with suitable packino' in top of the other, each unit supported by the insulating wall, Figure 5.

The top surface (32) of the dish-shaped member is level and parallel with the circular disk In operation, oil delivered upon the upper level surface of the dish-shaped member will spread wit-h maximum slowness, because of no declevity, to the circle forming the boundary of the circular area.

When the oil, thus filmed, attains the circumference or rim of the top surface and flows onward, it does not fall downward, but, by adhesion, clings to the lower surface (3l) of the dish-shaped member. Thus the member supports a line film of oil covering the surfaces on top and on bottom.

Hot as, entering from the central hole in the ower plate (9), Figure 2, sustains intimate contact with the oil ilm encasing the dish-shaped section (8) maximum intercourse follows, as the only course open for the gas to follow is around the edges and over the top surface of` the dish-shaped member. v

The upward push of the gas is as upon a roof. Such film disturbance as is caused by the onward rushing of gas, which results in dripping, causes precipitation upon the upward surface of plate (9), Fig. 2.

The only impediments encountered are the a series, these units are placed one upon y ingame parts of the member. The function of this member is to produce maximum intimacycontactbetween the 'oil andvgas.l i

rlhere isy supplied` at ythe, `top of the generator, B, through pipe (l0), Figjl, the oil delivered for treatment. rlhe pipe is equipped with one-way cock ,(11), and the oil supplied is delivered by compressor (12). Uil, thus delivered, passes in a state of fine filmentation from ilmenting member-tdv I l ioil ma'ss'A is afforded thegopportunity to ilmenting member in its downward journey.

Heated hydrogen-containing gas is intro-` duced into'generator (B) atthe lowerin'take`c` (5) and proceeds constantly upward passing 1 alternately through the central openings g' A n `tempferzfiture which produ ls'suliicient inoabout.- the Y f ficietfalso todi (33) in the disks and then encompassing the. film of oil around and y y filmenting member (8) over its top surface and through the'next higher central opening l molecu1e,tlie.-act of `via many hydrocarbon compounds.

the large range off'these differences.

introducing heated gas tat the lower intakeff (5), and introducing oil to be treated atrthe"A upper intake (10), the `oil proceeds downward, encountering the filming construction, vand the heated gas rises" in a close Contact counter-flow. -i lt is evident that with oil thus )ourneying gas with which it has had contact. Con'trari wise, the greater elevation attained by theA gas, the greater is vthe quantity of oil witliy whichthe gas has-had Contact.' The faitli'crl the oil journeys,l therefore, the greater, y p customaryprocedureisto. give it the maxibecomes its temperature. i

)lilith the gas, the higher it rises, the more heat it has imparted, and the cooler it becomes. vllt thus results that in operation, the coolest part of the generator is at the top, the hottest at thebottom, the two temperatures graduating into each` other throughout the vertical length of the apparatus. e

The condition developed is, that the oil introduced to treatment on its ,downward journey is subjected to ever-lincreasing` gra'- Operation presents certain considerations. Q

Crude petroleum is a conglomerate masslt is not homogeneous, but is a mixture l Each con-'5 stitueiit possesses distinctive characteristics,I varying one from the other' 'in boiling point,"' specific gravity, density, and temperature of nonstability. The mass is` rendered f urtlierv complex by carrying throughabsorption-tha most rareed 'off' gases, and' by' suspension some of the heaviest ofthe hydrocarbon group. laboratoryy analysis presents the different compounds making up the oil tion dation yof temperature, and the gas in its ascendency isjl subjected yto ,everfdecreasing temperatre .The 'eil' thus" experiences.' a gradual, yet fever-increasing temperature. When. any 011e., of ,the differenti@ dhyd'- choosev gneeded.r temperature for vaporizai andgin'ithisfsensefft fleration might be termed seleotivedistilla ion.

l""Vleiemit 4possibi@iii"all'instances, for the lecular `'actii'fityr oil, to be suf` ability of the p ing, in the presence @of hydrogencontaining gases, would result in hydrogenfincorporation and reduc- 'QO "specificlgravity However, certain compounds, later mentione fat vaporization temperatures exhibit sos 'gl ,an increase of inter-atomic movement be insufficient tion fto the point o The primarynecessi to unstabilize the paraiine', so additional ydrogen may be assimilated,- and this mustibe' accomplished .withyan lapparlatus.Msufliciently sensitive to adapt itself tothe varying l ,refquirements of {undergol treatinentgi "Customarilyitis said process oper- "presfsure, are chosen, the answer is that best results Iare foundftoobt'ain @under such condowiiward with an initial, comparatively l* l A cool temperature, and with hot gas -thi`1sf-:. journeying upward, the farther downward; the oil travels, 'the greater is the quantity ofi "be; iiouniform y'condition .to satisfy suoli "widely, differentiated requirements. At best, "a ilgle, condition; can vbe ,brit an average, a infthis tistoo-"great for certain requ'ii-ementsandfinsuflioient for others, The

mum requirement and let it go at that.

The table following is presented as the solution of our problem. ln it will be found molecular weights, vaporliaation teniperatures (boiling points),y aiidtempera tures of molecular instability.

rlhelastv of these Vis the degreeof heat at which ther stringsA ofattractinbetween the atomicl constituents, making the hydrocarbon molecule, are strained to afpointfof non# equilibrium. lt vis theoriticalftemperature for hydrogen absorption and molecular readjustment, the most favored condition for gravity reduction.

Carried to excess, however, with violent and ill-adjusted excess of heat, the atomic constituents break asiinder, even as the molecules separate in the process of vaporization. This excess' results in over-raieiication and carbonization.

high instability temperature; likewise in- Undeeane CiiH'ii a kerosene compound 381 Namdecane C19 4, a fuel oil compound.... 626

mate in the heavy compounds than in the light, and the transfer of energy produced by heat, is more eifectually made through the instrumentality of heavy mass than with the lighter construction of slight compara- 4"tive density. rlhe curve of this relationship is superposed as follows:

5 rlhe ourves cross' between p'entadecane'bl pressure needed to elevate the boiling point.

p. 51891K, and hexadeeandvb:-p.,550. All lighter compounds possess ylower.boiling points thanA tem eratures of'. instability; all heavier compounds areunstable before attaining boilingpoint.y I y y i v The last sliovvntable vincludes a list of pressure eoeflicientsby which the boiling temperatures of the compounds are .elevated to thetemperature ofin'stablity. t t The enormous; pressures indioated vfor the iist 'fewy compounds of theseriesare all within the gasoline group. v They... are set forth simply tovshoWthe intensity? of the arabolic curvey No operation, of course, iscontemplated .for the hydrogenization of these ooinpnindsl t The lightest of the laine ilyvlor. which treatment by the submitted process isgconsidered, would be decane, which is the lightestof .the kerosene series.

. The method for arrivingjat temperature and pounds pressurev` requirements for operation of .thesystem and apparatus submitn ted is: 4 L A Dleternine first the character of oil to be treated, bysimplel laboratory boil-over and condensation test; .carry the percentages to ank approximate dry... Compute tables ot readyreerence as above kEstimate the of the lightest component'of the .oil to a temperature equ'alling the temperature of instability for the 'particular compound. All' compounds :heavier than the lightest oceurreiit' in thepoil, will have lowerteinperar tures'oti'nstability. The result is,` that with the establishment of a'pressur'e which causes the lightest component to become unstable before vaporizing, this will effect instability in all components prior to their vaporiza- `tioIL .ln-easel of' ext" inelyl heavy petroleuins`7 or Irefinery"residual oils,y 'if `their boiling point "is 'above 525 degrees lyno pressure Whatever is needed because it has been shown that compounds possessing such a boiling point and over, attain the state of instability prior to boiling. y

The purpose ot this regulation, as is apparent, consists in establishing cor ditions so that 'when .the oil vaporizes, it v` b/orizes in a state of non-stability, in which condition it is susceptible to'inolec'ilar readjustnient and the incorporation ot the heatimparting and surrounding hydrogen-oarrying gases. v f

ln addition to the tabulated information for calculating pressurev and temperature requirements, is needed a table of saturated steam coefficients, contained in Kent or any other pocket manual. The reason is this:

Pressure is regulated. to raise the boiling point of the lightest compound to its temperature of instability, so that the vapor is unstable. This heat will eXceed'the instability temperature of all other fractions of the oil, rendering them unstable.

But: the pressure which raises the boiling point ofthe lightest compound possessing the lowest boiling point, has also raised the boiling point of the other hydrocarbons. The other hydrocarbons without additional heat, therefore, can not boil. The maximum and minimum .within the generator must be conditioned to serve all compounds in the oil, the selective feature of the operation giving each the desired equation, but all conditions must be furnished.

lVith instability established, boiling is not an absolute essential, but the operation is hastened by the intimacy of contact afforded.

The pressure condition is established by the pounds per inch needed to cause the lightest compound to unstabilize before vaporizing. The temperature condition is established by ascertaining a new boiling point for the compound requiring the greatest heat to Vaporize, under pressure conditions thus established.

The formula is:

h. c.:heaviest compound.

b. p.:heaviest compound boilingV point (0F).

P:pounds per square inch pressure.

S:s`team boiling point, same pressure.

T:maXimum required heat.l

:sped grav. h. o.+b' p This .formula is not submitted as completely accurate, but furnishes suiciently reliable an index for heat requirements to answer the necessities of practical operation,

Illustration.

: 1 :laboratory boil-over.

Below 3500: 0% 350-40o=i9% 400-5000:23% 50G-600014070 60o-7000215170 Over 7000: 3%

Pressure.

Maggio Illustration.

specific :2:laboratory boil-over.

Below 4500: 0% 150-5000: 18% 50G-6000 32% 60G-700 :30% 700750O:16% Over 7500: 4%

Pressure.

450-5000-tridecane; b. p. 4.53.20; temperature of instability 5900; pressure required to elevate boiling point to temperature of instability, 66.6 pounds. (Pressure 66.6:75 lbs.)

T empeature.

Over 7500-Tetracosane; b. p. 7880; specific gravity 0.7597; pressure 75 pounds.

S-212 32o-212 Q T S .gr. Lb 0.7597 +788 930 Fa temperature required.

The operations within the generator then, are as follows:

Theoil mass starts downward from its inlet; 10, maintaining a state of fine filmentation in the presence of the super-heated gases introduced at the gas intake, 5, at the bottom of the generator.

As the oil mass proceeds downward, en-A countering ever-increasing temperature, such hydrocarbon components as require the least temperature for vaporization, under the pressure conditions provided, are vaporized. Prior to the occurence of this vaporization, a temperature has been encountered equalling the state of instability, the state in which molecular equilibrium is disrupted. Thus, the vapor formed emanates in a state of molecular instability. In the presence of the heat-imparting, hydrogencontaining gas, equilibrium is sought be.- tween the two, resulting in mutual interchange, producing hydrogenization of the unstabilized, vaporized liquid.

Each successively heavier compound attains greater penetration of the generator. Attainment of each respective boiling point temperature vaporizes the particular compound, and insures its release from temperature in excess of that required. As a vapor, the oil rises to cooler zones. The resui'es, successively, are instebiiiiy, veporizeiion, and hydrogeoizeeion.

Through i'egiiiaio-n of the quantities of compaiaiveiy eooi oii ini'ociuced into the geneietoi", ehe quantities o hot gas introduced, end the temperature of the gases when introduced, iie iempei'eiure of the iop cimmbei, i3, othe generator, into which is attached the exit pipe, 14:, is seguizitebie.

Tinus, pi'esunfiingg die desiie; .oofiuct to e type of gasoline ivih en avenge 200 peine: the nest condision the oop oiismeei, i3, is segiiiete so 'siiis 'iemie, eonecfsed, iiowev, eog'ustsien piessuie cendi'ion niaineinlng. esui shes oniy siicli 1 ons e voieeiie 'ene seieesi awel honing' sie gouiiey oi ioohe she more siii-used of ''iie Ahem/'isi' i eeen eoinoound, wie mise-es' suir'iioiem iiyciiogen owe? point seiective einpeieft "so ehenbei, if: Toueies beiioie cii' ie'eeive-ienipeiesuie. Therese. 'M

l oii Afesunfies 'bine downward coni "W Revepoiseion occiws es vey 'iise sempei'hs'use iiioiigii i.

A sponge "ens Wn on s cook s'faov w' "e, s 500. susfsce heet, Wiii becomes cindei?, suspensie@L in e steam ieb, si "bhe eine einpemituie, saburetes. i heavy iiydiocsbon, squeezed with piessuie and ex cessive me'si-deiiveied hes-i3, iiiops cannon end gives ofi1 gas, but simuieteci by intinste conm-c with hot hydrogen-consomme; ges, seiiimtion follows.

it is, of course, apparent msi; eine opeis- Jxion outlined isnoi inieimitent, buit con inuous in the dfewin Fig. l, the receiving tank, @,'beiow ehe con ensei, C, receives the pisoduoso 'the operation. The eguietive diseiieige fiom the generator denies exit 53o sii else than e .vapor or gas at the selected emperetuie. Such o ibis es liqueies, hioligii the condenser, C, is pieoiptsed on the ioor is eken info ehe heide?2 pressure, to he ement of ine seems?. consumed, and incorporsteci, ouing spessi-ion, "Foe of ges hiougii sho genereoi* is in excess oi' j@he ieouiieinen'is ooi sive esoion Wiii ihe oii,

" ene any oii ini-'3roe composed of snob heavy con, iinpiiiities es noi; eo vagos., e fied s "i Lenin 16, "oeiow, i

The seine is and eutoff mise, f. desired :to pieoiioe ens pieeieimined sind mis esuia may loe y e number of I fiesen eeen govei'neci. by sT sowie um me empeszui'e p of ne genei'eoi o .ein desiifef. These i 'ses .feinsiiy of i se, es noci eondensing, in 'h-is psi erases, wiiises she expansion oi? :@eiessef pisseuse, supnienienicm q ne *gig- 3 eessying oifodiiegs o: Uiie genei'eioi, oesses hirongi encompassing'oise,i9, o erge? The joiooincs delivers@ pipe, ix, its s'mosgiiere of jeiow, so nos ne 'vepois oenvesited inio e the einen@ of 'heii cepeoisy' 'fao assieme such They see deiiveiecieebhe zeiininos, yin fhe eoiieciiig senin, i inst of ise ges which does I iiqiiey linen obtains outie iiiiougii *die i pipe, 15, which is equipped with a i nesse oiessuie oook, 2, so reguisssbie nes pennies disoiisige s mciion less pessuie the oressoie appearing in the top oi die generator, minus friction. it his point of disohs'ge, above the cock, 2, che pressuie is eieaseo end expansion eno-.Tof irigeieion 'eske piece.

-bien iis-"incisions, is dien conducted inem Ahe ges, having iseheiged its refiigem# element, scarcely needs description, as it consists simply of a tank constructed for the purpose, amply strong to withstand the required pressures. It is equipped with double discharge valves,` 2G, as in case steam has been used in the operation, quantities of Water will settle to the bottom. The entire apparatus is equipped with pyrometers, thermometers, liquid and pressure gauges, at the several appropriate and necessary points.

The compressor, 2, receives its gas supply from the gas-holder (not illustrated). The gas-holder receives the exhaust gas from pipe 22, augmented by gas supplied from outside sources as required.

Such details as the use of heated gas for Warming the crude oil before introduction into the generator, B, are not indicated, but it is to be understood that any suitable appliance for this purpose may be employed.

1t is to be understood that the foregoing description is merely one Way in Which the results indicated can be obtained from the principles involved in the operation of this particular apparatus. lt is not the purpose to give in exact detail the needs of a commercial apparatus operated on the principles indicated.

1t is to be further understood that many changes in the arrangement, order, and steps of the process and method, and in the apparatus as herein set forth, can be made Within the scope of the claims, 'and as indicated by the variations in the different claims, Without departing from the spirit ot the invention.

There is submitted an apparatus consisting mainly of a ire-clay-lined shell, equipped Within Withcertain oil tilmenting members.

By the introducing of relatively cool oil at the top, and heated, hydrogen-containing gas at the bottom, the counter-flow of the two is designed to make the top of this generator the coolest, and the bottom the hottest. Thus conditioned, the farther the oil penetrates toward the bottom of the generator, the greater is the heat experienced, and the higher the gas rises, the cooler are the zones it encounters.

This is based upon the premise of the clomplex character of petroleum or its heavier1 fractions, in that their composition is one of a mixture lof differentiated hydrocarbons. The purpose is that, by continuous operation, as the boiling point of any particular compound is reached in temperature, because of the fineness of its lmentation, vaporization follows, and the vapor ascends to cooler zones, each compound being permitted, in this Way, the opportunity to select its needed temperature for vaporization.

iai-2eme There is presented, as the needed pressure equation, the degree of pressure needed to raise the boiling point to the temperature of instability of the molecule constituting the most raretied ot the petroleum mass undergoing treatment. This fraction is determined by simple laboratory boil-over analysis. The heat equation is determined by the temperature needed to boil the heaviest frac'- tion under the pressure condition thus established.

The principle of this regulation is that when vaporization occurs, each respective compound Will vaporize in a condition of non-stability, enabled thereby to undergo molecular readjustment in the presence ot' the hydrogen-containing gas, which adds to its hydrogen content, producing lower boiling point and specific gravity. The top regulative chamber is maintained at such temperature, taking into consideration the pressure regulation, as to permit only in the form of vapor, exit oit hydrocarbon compounds susceptible of maintaining the state of vaporization under the lconditions maintained.

The results claimed is that the operation .of the generator makes possible pre-deter mination of the product to be delivered, and the gradation of temperature administered, gives to each constituting carbon of the oil mass the selective temperature needed for unstabilized vaporization, and hydrogenous incorporation.

There may be employed, in this operation, anyohydrogemcontainng gas; for instance,

natural gas, overly rareied products offra@ tional distillation, or other retiery'proc esses; artificial gas, particularly Water gas, containing upwards of fifty per cent, by volume, in hydrogen; free hydrogen as a derivative, for instance, of super-heated steam in contact With metallic, oxidizing reagents, or otherwise.

Theremaining parts of the apparatus, consisting of gas super-heater, condensation coils, reception tank for product delivered, and gas-holder, are merely adjuncts necessary to the operation of the generator, and may be of any suitable type.

Tt might also be added that any hydrocarbon compound of the oil mass, unable atinitial vaporization to become sulliciently hydrogenized to maintain vapor state at the regulative temperature of the topmost' regulative chamber, lique'es in the cooler Zones before attaining this chamber, and is thus subjected to re-vaporization, the process being re eated until adequate hydrogenization is ha to enable the compound in its new form to pass the requirements of the regulative chamber.

The time element needed for all reactions is increased, when need be, by elongation vertlcally of the generator, and an increase in the number of ilmenting members.

Distinguished from crac/ving.

Customarily, cracking is a term applied to a process involving an active state of a heated oil mass, in which pronounced dismemberment is in progress. The scope of the word, in some instances, has been enlarged to include the products of the process: rare gas, carbon depositing, and lower specific gravity of the residue. rlhe process submitted is not cracking.

ln cracking, the temperature is so intensive that inter-atomic agitation is carried beyond the point ot molecular instability, to molecular dismemberment.

The process submitted contemplates no severance of the constituting hydrogen and carbon, but the principle involved finds entire application during the period of molecular instability.

A n apparatus constructed and operated in accordance with the process presented, constantly aii'ords opportunity for hydrogen increase in the oil mass, simultaneously with attainment by an constituting compound of sucient instabllity for its reception. As the oil constituents penetrate farther and farther into the apparatus and into greater heat, each diderentiated memberencounters itsrequired temperature for the purpose. increase 0'1": hydrogen content lowers the boiling point, and immediate relief, as vapor, is had from the excess temperature which rends asunder the molecule. The essence of this process is notto crack.

The comparison4 requires, possibly, reference to the readjustment occurrent in cracking. How can the dismemberment or cracking, of a, molecule, composed of hydrogen and carbom'resulting in the release of its carbon asa solid, and, of its vhydroven'as a gas, decrease thespeciic gravity ot the oil mass undergoing ltre atment? y `y kThe'happejning'is vthis Byapplication of heat and pressure conditions, certain vcom-` poundsy areburst asunder; ,carbon is precipitated as a's'olid, andthe hydrogen which had been unified with it tfmake a hydrocarbon, is'released. This released hydrogen, taking advantage of the stirred-up condition of the other hydrocarbons, vjoins them, forcing its way into other molecules because of their receptivity produced by temperature and pressure. rlihis entrance foi hydrogen increases the hydrogen content`,-reducing thereby speciiic gravity. The. molecul'ein a state of agitation is. increasing its hydrogen content.

it must be'remembered' that the higher the boiling point, the lower t'hepcracking point. Thus, in cracking -processes, ,the moiecules' constitutingthe heaviest hy we l carbcns, reach `the pointoih such intensitied oscillation as to burst asunder. Their carbon is deposited, their hydrogen in corporated by members of lower boiling point and higher cracking point.

lThe new hydrogen lncorporation still further lowers the boiling point, and increases the dismemberment temperature for the molecule, so that the heavier constituents are hydrogenizing the lighter.

llhe cracking process is the dismemberment of the heavy for the hydrogenization of the lighter, the active agency lying in the dismemberment in cracking. )In the process presented, hydrogenization is otherwise provided to the unstable molecule, and the essence is not to crack.

ln the process submitted, the state of receptivity is established in which hydrogen is assimilative, and the hydrogen is supplied. @ne is destructive, the other constructive conversion.

rlhe apparatus submitted 'is virtually selfregulative. Arrange the requirements of the'two extremes of the oil-constituting compounds, and each constituent chooses its own requirements.

Cracking apparatuses, in their various forms, impose conditions based upon dis' membering, or cracking, certain parts of the oil mass, while no such conditions are present in apparatuses operated by this process.

it is important to note that, as cracking effects the elimination of certain fractions, the residuary bulk is of decreased amount. rlhe method proposed adds to the bulk, making greater quantity as the specific gravity is` reduced.

Oil sample, weight per gallon '7.21 pounds.

i Gas sample, by volume 250 cubic feet.

Methane CHi 2035633 =9 1bs.=,6.75 lbs. 2.251lis.

' 4 seins. 2.391135.

` 12.30lhs.

l..5-l ll)SY 3.97 lbs. 195i llJS.

Reaction.'

Gasoline series: v n

ramene-05net.?. casu 2.41m.: 2. ins. i im. HQXQUG CSHH I 153.21'.l.0 L'10. f 2 Heptanc (21H15 209. 2.3 f 2.2iA .46 OCLHO 05H13 i 25S. 1.5 n 1.2 .3 H

` i 15.54 its. aieibs.- favours.

Free hydrogen .31 lbs.

wel lbs.

Quantities: .7 5 2.5 gallons gasoline+ .81 lbs. hydrogen.

It should be mentioned that great saving is found in the use of the methods and type ot apparatus presented, as a substitute for the usual checker-brick form of carburetor as incorporated as part of the standard equipment for generating artificial gas.

Generator B is incorporated between the gas generator and superheater of the ordinary sets, ll. G. lVilkinson and others.

The heated gas from the gas generator is delivered at the. bottom of' generator B, and the oil to be used for enrichment purposes at the top, through pipe 10. No pressure is required. The vaporized oil and gas introduced enter the superheater of thel set through pipe 1l, where fixation occurs.

The term hydrogen-containing gas as used herein means a gas or vapor in which hydrogen is occurrent either in a free. state or in chemical combination.

The process presented will be referred to in the claims as constructive conversion because by its use hydrocarbon compounds are converted into others by a constructive method of addition in contrast to the destructive method of substraction or cracking.

The phrase carbon deposit as used means carbon as deposited by molecular dismembe-rment or cracking of the hydrocarbon compounds.

In the phrase a process for the constructive conversion of hydrocarbons ot higher boiling points and hydrogen containing gases Vinto liquid hydrocarbons of lowfer boilin points the words hydrocarbons of hig er boiling points and hydrocarbons of lower boiling points, both refer to hydrocarbons which are liquid at atmospheric pressure and temperature.

The -expression substantially homogeneous product as used does not mean that the compounds ot the hydrocarbon product shall have the same boiling points. I refer to such a product as commercial gasoline as a substantially homogeneous product, although some of its constitutent compounds have boiling points as low as approximately 100O and others as high as approximately :2800.

The term pressure as used in the claims is intended to mean pressure above atmoshere.

The thickness ot the oil films in the ap- Maggio paratus will be determined by the viscosity of the oil, as will readily be understood.

It will be understood that in using unreiined petroleum and flowing the same into the increasing temperatures there is first vaporized in substantially lan unchanged state the gasoline content of the petroleum.

Referring to increase ot the hydrogen content of the hydrocarbon molecules; it is apparent that when the boiling point ot the lightest hydrocarbon compound of an oil is raised to its corresponding instability temperature all of the members ot the series possessing higher boiling point must have been raised to or beyond their instability temperature because as the boiling points increase instability temperatures decrease.

The operation of the process submitted includes hydrogenization ot the heavier compounds of the oil undergoing treatment at temperatures less than that of their respectively advanced boiling points. By this operation it becomes apparent that through increase of the hydrogen content of such compounds their boiling points become reduced and vaporization effected.

What is claimed as new is 1. A process for the constructive conversion of hydrocarbons ot higher boiling points and hydrogen containing into liquid hydrocarbons of lower boiling points, which consists in successively subjecting, in a confined space, each liquid hydrocarbon compound under pressure to constantly increasing temperatures sufficient to produce substantial molecular instability and through maintenance of intimate contact between the liquid hydrocarbons and hydrogen-containing gas, preventing dismemberment or cracking by effecting hydrogen incorporation into the hydrocarbon mass, thus lowering the boiling points of" the hydrocarbon compounds and vaporizing the same and conducting the vapor through zones of decreas\ing temperatures and so conditioning the operation that substantially the entire oil mass is bonverted into a. substantially homogeneous product.

2. A process t'or the constructive conversion of hydrocarbons of` higher boiling points and hydrogen containing gas into liquid hydrocarbons ot lower boiling points. which consists in successively and continuously subjectino', in a confined space, each liquid hydrocarbon compound under pressure to constantly increasing ten'ipcratures sufficient to produce substantial molecular instability and through maintenance of intimate contact between the liquid hvdrocarbons and hydrogen-containing gas` preventing dismembernient or cracking b v eiiecting hydrogen incorporation into the hydrocarbon mass, thus lowering the boiling points of the hydrocarbon compounds and vapor- Maaate izing the same and conducting them through zones of decreasing temperatures and so conditioning the operation that substantially the entire oil mass is converted into a substantially homogeneous product.

3. A process for the constructive conversion of hydrocarbons of higher boiling points and hydrogen containing gas into liquid hydrocarbons of lower boiling points, which consists in commingling in a confined space hydrocarbons in liquid and vapor states -and a hydrogen containing gas, filming the liquid hydrocarbon and administering heat thereto, through the medium otl the hydrogen-containing gas and vapor, under regulations of temperature and pressure, so that suiiicient molecular instability is established for each compound to undergo hydrogen incorporation without cracking, and so regulating exit conditionsl that-only a predetermined and substantially homogeneous product may escape.

1l. A process for the constructive conversion of hydrocarbons ot higher boiling points and hydrogen containing gas into li uid hydrocarbons of lower boiling points, willich consists in commingling hydrogen containing gas in a confined space with hydrocarbons in liquid and vapor states` causing sufficient molecular instability solely by regulation of temperature and pressure to produce molecular re-adjustment and increase of the hydrogen content of the heavierl compounds, without molecular' dismemberment or cracking, subjecting the resulting hydrocarbon vapors to decreasing temperatures, and maintaining such regulation of exit conditions that only, a substantially homogeneous hydrocarbon may escape.

- A process Jfor the constructive conversion oi hydrocarbons of higher boiling points and hydrogen containing gas into liquid hydrocarbons of lower boiling points, which consists in establishing, in a confined space, a counter flow of heated hydrogen containing gas, carrying hydrocarbon vapors, against relatively cool oil, filmed to tineness, so that the oil flows into increasing temperatures and the and vapor into decreasing temperatures, with regulation of heat and pressures so that, through heat absorption, oil compounds acquire suliicient molecular instability to cause increase of their hydrogen-content and molecular rc-adjustment, thus eli'ecting the lowering of boiling points, the hydrocarbon vapors, in this manner, not being permitted to attain suicient temperature for molecular disruption and carbon deposit.

ti. A process for the constructive conversion of hydrocarbons of higher boiling points and hydrogen containing gas into liquid hydrocarbons of lower boiling points, which consists in bringing togetherm'ii. ay confined space, an oil, a hydrogen-contaihing gas and hydrocarbon vaporsv so that intimate y contact is established between the oil and the gaseous material, by flowing `the oil vdownward in a state of fine filmentation, against the gas, with heat and pressure conditions so adjusted that maximum temperature voccurs at the lowermost filmenting member and minimum at the uppermosty the degree of heat and the amount of pressure being so adusted and supplied that the boiling points ot' the liquid compounds are retarded to equal or exceed a temperature at which interatomic activity is sufficiently accelerated to cause molecular readjustment and incorporation of the lighter surrounding gaseous materials without dismemberment or cracking, whereby the volume of the liquid hydrocarbons is increased through constructive conversion to the extent of the incorporaton of the more rarefied materal.

7. The. process for the constructive conversion of hydrocarbons ot' higher boiling points and hydrogen containing gas into liquid hydrocarbons of lower boiling points, which consists in filming a hydrocarbon oil in a vertical reaction chamber, over a plurality of filming members, adapted to retain oil on their upper and lower surfaces, the thickness of said film being conditioned only by the viscosity 'of the oil, and the general direction of flow being downward and simultaneously introducing into said vertical reaction chamber, a heated hydrogen containing gas, causing said gas to flow around and across the films of the oil in a general direction contrary to that of the films, under adequate pressure, said gas through its passage heating said flms of oil to their 'respective instability temperatures, thereby causing some of the hydrogen containing gas to combine with the oil without carbon deposit and subsequently vaporizing the oil.

8. The process tor the constructiveconversion ot' hydrocarbons, ot' higher boiling points and hydrogen containing gas into liquid hydrocarbons of lower boiling points, which consists is establishing,` in a confined space, the presence of hydrogen-containing gaseous material and non-gaseous hydrocarlions and successively and continuously/heating each compound ot' the non-gaseous hydrocarbon to a temperature ot' molecular instability by regulation of heat and pressure conditions, and maintaining intimate contact between the gaseous and non-gaseing temperature and so conditioning the operation that substantially the entire nongaseous hydrocarbon is converted into a substantially homogeneous product.

9. The process for the constructive conversion of hydrocarbons, of higher boiling points and hydrogen containing gas into liquid hydrocarbons of lowerl boiling points, which consists in substantially and continuously unstabilizing hydrocarbon oil, or its fractions, solely by means of heat and pressure, at a temperature insufficient to crack any constituent of the same and combining added hydrogen with the unstabilized hydrocarbon, thereby converting the hydrocarbons into compounds of reduced specific gravity and lower boiling points capable of vaporizing as a substantially homogeneous product.

10. A process for converting, by constructive conversion, practically the whole of a hydrocarbon mass into gasoline of predetermined grade, which consists in introducing into a confined space, petroleum or its heavier fractions and hydrogen containing gas, so conditioned7 that the course followed by the oil is into increasing temperatures and lthe course followed by the gas is into dccreasing temperatures, so that intimate contact is maintained between the oil and the gas; the temperature and pressure conditions being so regulated that each volatilizable compound of the oil, without being cracked, has its boiling point advanced beyond the temperature at which molecular instability is suiiicient for molecular readjustment and incorporation of lighter substances from the surrounding hydrogen containing gas and so that passage through the exit is denied to all compounds unable to maintain a vapor state at the predetermined boiling point of the selected grade of gasoline, said compounds being condensed amil caused to repeat the sequence of instability, hydrogenization and vaporization until exit requirements are met, the whole of said operation being carried on in such manner that hydrocarbon compounds are not dismembered or cracked in the process.

ll. A process of making gasoline out of various volatilizable liquid hydrocarbons heavier than gasoline which consists solely by means of heat and pressure in substantially and continuously unstabilizing without cracking the same andv in increasing the hydrogen content thereof at the point of molecular instability by supplying added hydrogen without carbon deposit by molecular disruption, whereby substantially all the liquid hydrocarbons are converted into gasc une.

l2. i process for the manufacture of gasoline irom various volatilizable liquid hydrocarbons of higher boiling points and ydrogen containing gas, which consists in heating the gas under sufhcient pressure and temperature to unstabilize those constituents of the liquid, having the highest boiling points, subjecting the liquid to the action of the heated gas in al confined ieaction zone, under conditions of pressure so that the compounds of the liquid are unstabilized without being cracked and their hydrogen content increased and then withdrawing substantially all the volatilizable hydrocarbons as gasoline vapors.

13. A process for producing gasoline from crude petroleum, which consists in introducing the petroleum and a hydrogen containing gas into a confined space, causing the two to counter-flow in intimate contact and under regulations of increasing temperature for the oil and decreasing temperature for the gas and under pressure so that there is first vaporized in substantially an unchanged state the gasoline content of the petroleum, the hydrocarbon compounds contained in the petroleum, which are heavier than those of the gasoline series, being subjected to regulation of heat and pressure, so that sufficient molecular instability is produced to cause molecular re-adjustment and increase of hydrogen content without dismemberinent or cracking by combining of the light and heavy compounds, within the confined space, the said compounds being converted into compounds of the gasoline series, and then withdrawing substantially the whole volatilizable aggregate of compounds as a gasoline vapor of the predetermined. class and variety.

14. The process for the constructive conversion of hydrocarbons of higher boiling points into gasoline, which consists in introducing petroleum or its heavier fractions and hydrogen containing gas into a confined re-Aaction zone, employing pressure and successively increasing temperatures on the oil t-o cause combination of the volatilizable substances so introduced by so conditioning the heat and pressure utilized that the boiling points of the liquid hydrocarbons are retarded to such extent, that prior to attainment of the retarded vaporization temperatures, suficient molecular instability is attained for molecular re-adjustment and securement of increased hydrogen content, and so that escape is denied all compounds, having a higher boiling' pointthan that of the heaviest constituting compound 'entering into the composition ol a selected grade of gasoline thus being manufactured, and so that any vapor denied exit is subjected to further hydrogenization, until able to conform with the established exit requirements, and so that attainment of molecular disruption and cracking does not occur,

lin testimony whereoi2 l have ailined my signature.

HARLD it.

iai 

